Allyl esters of fatty acids



Patented Jan. 2, 1951 ALLYL ESTERS OF FATTY ACIDS Maxwell A. Pollack, Denville, N; J., assignor to E. F. Drew & 00., Inc., New York, N. Y., a corporation of Delaware No Drawing. Application September 23, 1946, Serial No. 698,875

6 Claims.

The present invention is directed to esters of fatty acids, more specifically to esters produced by the use of various allyl alcohols.

Esters of fatty acids, particularly of mixtures of higher fatty acids obtained from natural fat oils having drying properties have been used in paints, varnishes and the like. Usually such esters are the glyceride esters of the fatty acids or esters of polymerized higher fatty acids. While such compositions have been found satisfactory in use as drying constituents of the coating compositions, a number of such esters particularly when derived from certain oils, have relatively poorfilm-forming characteristics. Among such materials are soya bean and cottonseed oils.

The present invention is intended to improve oils having poor film-forming characteristics and to provide esters of fatty acids occurring in certain fatoils to make them more useful in coating compositions.

,It is also among the objects of the present invention to modify drying oils with the formation of esters which are superior to the original drying oils for use in paint products and the like.

It is still further among the objects of the present invention to provide compositions containing the esters of the present invention in order to provide superior baking enamels and other heat cured compositions.

The present invention is based on the finding that when natural fat acids are esterified with an allyl alcohol, the polymerizability of the products is greatly enhanced over the original acids or their natural esters, such as the glycerides.

Allyl esters of fatty acids may be made in a number of different ways. For example, the fatty acid and allyl alcohol may be heated together, with or without added catalysts, such as sulfuric and benzenesulfonic acids, to form the esterdirectly. Also, other esters of the fat acids, such as the natural glycerides, may be converted to the allyl ester by treating with allyl alcohol in the presence of a suitable catalyst, such as sodium hydroxide. The esters may also be made from the allyl alcohol and the fatty acid chloride or anhydride.

Besides allyl alcohol, one may use other unsaturated alcohols, such as alpha-methylallyl alcohol, crotyl alcohol, butadienyl glycol, propargyl alcohol, and others. Preferably the alcohol is one having from 3 to carbon atoms, although allyl alcohols having a greater number of carbon atoms may also be used. The alcohol may have a plurality of double bonds.

The fat acids included in the invention are preferably those with a high degree of unsaturation. such as linoleic, linolenic, eleostearic, and the like, or natural or synthetic mixtures containing these. The invention contemplates oleic, ricinoleic, or even saturated acids such as stearic, lauric, caprylic, and the like. In the latter instances, prior compounds containing these acids ordinarily show no tendency to polymerize, whereas the esters of these same acids with allyl alcohols are found to possess definitely enhanced polymerization tendencies.

An important group of acids included in this invention is that obtained by the polymerization of unsaturated fat acids or their esters, such as the glycerides. For example, when soybean or linseed oils are heated at temperatures in the neighborhood of 300 C., polymerization occurs to give what are commonly known as the bodied oils. Actually, these oils consist of a mixture of polymerized and unpolymerized acid ingredients. In this reaction, the acid groupings which are actually polymerized lose substantially all ability to polymerize further. Now I have found that if these products are converted to the allyl esters, they become capable of undergoing further polymerization, which probably occurs through the allyl groupings. Further, the allyl esters of the polymerized acids can be separated substantially completely from the esters of the unpolymerized portions (by distillation, solvent separation, precipitation, etc.) to give new compositions of matter comprising diallyl and other polyallyl esters of polymerized fat acids.

These productscan polymerize further to give I strong and insoluble films or massive objects, either by themselves, or in admixture with other polymerizing ingredients, such as drying oils, synthetic resins, such as alkyd, phenolic, urea, etc., or styrene, methyl methacrylate, allyl methacrylate, and the like. Further, they may be used as vulcanizable plasticizers in rubber compositions, in nitrocellulose lacquers, and the like.

These esters can also be utilized in a wide variety of other ways. For example, they may be used as elastomers. In particular, the allyl ester of polymerized fat acids may be used to produce elastomeric materials by polymerization, followed by vulcanization. Elastomeric or rubber-like products may also be prepared by copolymerization of the allyl esters with compounds such as butadiene, styrene, vinyl chloride, acrylic acids and esters, and the like. Plastics or elastomers obtained from allyl esters may also be used for gaskets, sealing compounds, adhesives, coatings for paper, textiles, leather, etc.

l esters, in particular, the esters of th i d g'ing acids, including the saturated acids, have wide utility as plasticizers and softening modifiers, and may be used in textile coat ings, wire coatings, synthetic rubbers, sheeted, calendered, and molded goods, plastics, and in general, wherever a softening action may be ed. i l irious methods may be used for making the esters of the present invention, and the following examples typify some of the methods which may be used in practicing the same.

Example I.All:ul esters of soya acids A mixture of 250 parts of refined soybean oil, 500 parts of allyl alcohol, and one part of solid potassium hydroxide is heated under a reflux for three hours. The catalyst is discharged by the addition of two parts of concentrated hydrochloric acid, and the excess allyl alcohol removed by distillation. The residue is washed four t.mes with distilled water to remove glycerine, salt, and any residual allyl alcohol. The washed product is dried in vacuo on a boiling water bath, giving 248 parts of a fluid, amber-colored ester of soya acids, with an iodine number of 196.

Example II.AZlyl esters of linseed acids A mixture of one mol. of linseed fatty acids, five mols. of allyl alcohol, and 0.1% of p-toiuenesulfonic acid is heated under a fractionating column, and the constant boiling mixture of allyl alcohol and water is removed. When all the water is over, the excess allyl alcohol is removed by further distillation, and the liquid residue is washed several times with dilute alkali and water, to remove the catalyst. The neutral product is dried in vacuo, leaving a clear, amber-colored liquid, which are the allyl esters of linseed acids.

Example III.Allyl esters of bodied soy bean oil Refined soybean oil is heated at about 300 C. in an atmosphere of carbon d.oxide for about 24 hours, giving a bodied oil containing approximately 40% of polymerized ingredients.

Five hundred parts of this bodied 0.1 is mixed with 1000 parts of allyl alcohol and 2.5 parts of sodium methoxide in 33 parts of methyl alcohol, and the mixture refluxed for about three hours, whereupon one homogeneous clear system is formed. The catalyst is then discharged with parts of concentrated hydrochloric acid, and the excess allyl alcohol removed by distillation at an internal temperature in the liquid of 160 C.

After cooling, the product is washed four times with 200 parts of distilled water, and dried in vacuo on a boiling water bath. The product is clear, red-brown in color, and has an iodine number of 155, while the bodied oil from which it had been derived had an iodine number of only 98.

Example IV.Separation of allyl esters of polymerized and unpolymerized soya acids Two hundred and fifty parts of the product of Example III is distilled under reduced pressure (8-11 mm. of mercury), collecting 128 parts of distillate largely between 180 and 190 C. under a pressure of 8 mm. The distillate is light yellow in color, highly fluid and has an iodine number of 158, while the residue is darker, more viscous, and has an iodine number of 144. The residue is the allyl esters of polymerized soya acids.

The superiority of the present products is illustrated by comparative tests made thereon. For

instance, when the ester made from bodied soya bean oil, as set forth in Example 111 is heated for six hours in an atmosphere of carbon dioxide at about 290 to 295 C., it shows an increase in viscosity of about 530%. Similarly, when the products obtained from polymerized soya bean fatty acids, as set forth in Example IV, are treated in the same manner, it shows an increase in viscos.ty of about 480%. This compares with a increase in viscosity of refined soya bean oil when treated under identical conditions.

The allyl ester of polymerized soya bean fat acids is heated at about 280 to 315 C. in an atmosphere of air, whereupon it is converted to a gel in about 53 minutes. Soya bean oil may be heated for a considerable number of hours under the same conditions, as for instance overnight, and no substantial amount of selling will take p ace.

In air-blowing tests at 150 0., the allyl esters of the polymerized as well as the unpolymerized soya acids showed greater percentage increases in viscosity than the original refined soybean oil from which they were derived.

A coatin composition made with an allyl ester of polymerized soya bean fatty acids may be coated upon a suitable surface and dried. The film is then baked in an oven at 100 0. whereby the film is converted into a tough, strong and tack-free product, which is resistant to weathering and abrasion. Excellent results v are obtained by incorporating said allyl esters in alkyd resin baking enamels. The amount of the esters added to the enamels or other coating compositions may vary widely. In many cases the esters may be substituted in whole or in part for the resinous material in the film-forming composition.

Although the invention has been described setting forth several specific embodiments thereof, the invention is not limited thereto. Various other allyl type alcohols than those specifically named may be used. Single fatty acids or mixtures other than those set forth herein are equally suitable for the purpose. The number of carbon atoms in the fatty acids may vary between 6 and 20, and the acids may be saturated or unsaturated. The source of the acids may be animal or vegetable. Not only natural fat acids but synthetic acids having a suitable number of carbon atoms, whether even or odd, are suitable for the production of the esters of the present invention. The details of the procedure for producing esters may be greatly varied and. other methods such as are known in the art may be utilized.

From the above, it will be apparent that the invention is relatively broad and is to be broadly construed and not to be limited except by the claims appended hereto.

I claim:

1. A method of makin modified oils having valuable film forming and drying properties which comprises heating a drying oil to a temperature in the neighborhood of 300 C, for a suflicient length of time to cause partial polymerization of unsaturated acids to take place, alcoholizing said oil so polymerized with an unsaturated monohydric alcohol having 3 to 10 carbon atoms, and heating said unsaturated alcohol ester at about 300 C. for a sufiicient length of time to increase the viscosity of said product.

2. A method of making modified oils having valuable film forming and drying properties which comprises heating a drying oil to a temmerization perature in the neighborhood of 300 C. for a sufllcient length of time to cause partial polymerization of unsaturated acids to take place in the presence of an alkali metal alcoholate as catalyst, alcoholizing said oil so polymerized with an unsaturated monohydric alcohol having 3 to carbon atoms, and heating said unsaturated alcohol ester at about 300 C. for a sufficient length of time to increase the viscosity of said product.

3. A method of making modified oils having valuable film forming and drying properties which comprises heating a drying oil to a temperature in the neighborhood of 300 C. for a suflicient length of time to cause partial polyof unsaturated acids to take place, alcoholizing said oil so polymerized with an unsaturated monohydric alcohol having 3 to 10 carbon atoms, separating and recoverin the unsaturated alcohol ester of the polymerized portion of said oil, and heating said ester at about 300 C. for a suiilcient length of time to increase the viscosityof said product.

4. A method of making modified oils having valuable film forming and drying properties which comprises heating a drying oil to a temperature in the neighborhood of 300 C. for a suflicient length of time to cause partial polymerization of unsaturated acids to take place, alcoholizing said oil so polymerized with an unsaturated monohydric alcohol having 3 to 10 carbon atoms, distilling said ester under reduced pressure to remove the unpolymerized portion and to obtain the unsaturated alcohol ester of the polymerized portion of said oil, and heating said ester at about 300 C. for a sufflcient length of time to increase the viscosity of said product.

5. A method of making modified oils having valuable film forming and drying properties which comprises heating soya bean oil to a temperature in the neighborhood of 300 C. for a suflicient length of time to cause partial polymerization of unsaturated acids to take place, alcoholizing said oil so polymerized with an unsaturated monohydric alcohol having 3 to 10 carbon atoms, and heating said unsaturated alcohol ester at about 300 C, for a sufiicient length of time to increase the viscosity of said product.

6. A method of making modified oils having valuable film forming and drying properties which comprises heating linseed oil to a temperature in the neighborhood of 300 C. for a sufiicient length of time to cause partial polymerization of unsaturated acids to take place, alcoholizing said oil so polymerized with an unsaturated monohydric alcohol having 3 to 10 carbon atoms, and heating said unsaturated alcohol ester at about 300 C. for a sumcient length of time to increase the viscosity of said product.

- MAXWELL A. POLLACEZ.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,218,439 Rothrock Oct. 15, 1940 2,249,768 Kropa July 22, 1941 2,305,228 Woodhouse et a1. Dec. 15, 1942 2,318,959 Muskat et a1. May 11, 1943 2,341,060 Price Feb. 8, 1944 2,356,871 Moflett et a1 Aug. 29, 1944 2,369,689 Robie Feb. 20, 1945 2,373,015 Cowan Apr. 3, 1945 2,378,827 Bradley June 19, 1945 2,441,023 Larsen May 4, 1948 

1. A METHOD OF MAKING MODIFIED OILS HAVING VALUABLE FILM FORMING AND DRYING PROPERTIES WHICH COMPRISES HEATING A DRYING OIL TO A TEMPERATURE IN THE NEIGHBORHOOD OF 300* C. FOR A SUFFICIENT LENGTH OF TIME TO CAUSE PARTIAL POLYMERIZATION OF UNSATURATED ACIDS TO TAKE PLACE, ALCOHOLIZING SAID OIL SO POLYMERIZED WITH AN UNSATURATED MONOHYDRIC ALCOHOL HAVING 3 TO 10 CARBON ATOMS, AND HEATING SAID UNSATURATED ALCOHOL ESTAR AT ABOUT 300* C. FOR A SUFFICIENT LENGTH OF TIME TO INCREASE THE VISCOSITY OF SAID PRODUCT. 